Substituted phenyl carbamates and their use as herbicides

ABSTRACT

Substituted phenyl carbamates of the formula ##STR1## in which: R is a member selected from the group consisting of halogen, trifluoromethyl, cyano, NO 2  and C 1  -C 3  haloalkyloxy, 
     R 1  is methyl or ethyl; 
     R 2  is independently selected from the group consisting of cyano, halogen, C 1  -C 4  alkyl, C 1  -C 4  alkoxy and C 1  -C 4  haloalkyl; and 
     n is the number of R 2  substituents and equals 1-5; 
     and their use as herbicides are disclosed herein.

This is a continuation of application Ser. No. 07/569,684 filed Aug. 20,1990 (abandoned).

BACKGROUND AND SUMMARY OF THE INVENTION

This invention relates to substituted phenyl carbamates, a process forproducing them and their use as herbicide intermediates. In particular,this invention relates to substituted phenyl carbamates of the formula##STR2## in which: R is a member selected from the group consisting ofhalogen, trifluoromethyl, cyano, NO₂ and C₁ -C₃ haloalkyloxy;

R₁ is methyl or ethyl;

R₂ is independently selected from the group consisting of cyano,halogen, C₁ -C₄ alkyl, C₁ -C₄ alkoxy and C₁ -C₄ haloalkyl;

n is the number of R₂ substituents and equals 1-5.

The compounds of the present invention, as will be seen from thedescription and test data which follows, have utility in preparing bothpre-emergence and post-emergence herbicides useful against a wide rangeof plant species. The compounds are of particular interest when used inpre-emergence application.

The terms "herbicide" and "herbicidal" are used herein to denote theinhibitive control or modification of undesired plant growth. Inhibitivecontrol and modification include all deviations from natural developmentsuch as, for example, total killing, growth retardation, defoliation,desiccation, regulation, stunting, tillering, stimulation, leaf burn,and dwarfing. The term "herbicidally effective amount" is used to denoteany amount which achieves such control or modification when applied tothe undesired plants themselves or to the area in which these plants aregrowing. The term "plants" is intended to include germinant seeds,emerging seedlings and established vegetation, including both roots andabove-ground portions.

DETAIL DESCRIPTION OF THE INVENTION AND PREFERRED EMBODIMENTS

Within the scope of the above formula, certain embodiments arepreferred, as follows.

R is preferably trifluoromethyl.

R₁ is preferably ethyl.

R₂ is preferably H, halogen C₁ -C₄ alkoxy and C₁ -C₄ haloalkyl.

The term "alkyl" and all groups containing alkyl portions are intendedto include both straight-chain, branched-chain and cyclic groups.Examples are methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl,t-butyl, 2-methyl-n-butyl.

The terms haloalkyl and haloalkyloxy refer to the alkyl and alkyloxygroups, respectively, substituted by one or more halogen atoms.

The compounds of this invention are prepared by the followingprocedures:

A) General Method of Preparation 1) Preparation of the IntermediatePhenoxyalcohols

The phenoxyalcohol intermediate is prepared by reaction of theappropriate phenol with the appropriate epoxide in water or dimethylformamide using a basic catalyst. The reaction is run at the refluxtemperature of the reaction mixture. Usually excess of the epoxide isrequired to react completely with the phenol. Potassium hydroxide at alevel of 10 mole percent is convenient to use as the basic catalyst.However, other basic catalysts can also be used instead of the potassiumhydroxide.

The product phenoxy alcohol separates from the reaction medium and canbe worked up with aqueous base to remove unreacted phenol and then driedover a drying agent and concentrated to remove any unreacted epoxide.

2) Preparation of the Intermediate Phenoxy Chloroformates

The intermediate phenoxy chloroformates are prepared by reaction of theappropriate phenoxyalcohol with excess phosgene in an inert solvent suchas methylene chloride in the presence of a catalytic quantity ofdimethyl formamide. The reaction is carried out at 20°-80° C. Thesolvent and excess phosgene is then removed under vacuo to give thedesired intermediate phenoxy chloroformate.

B) Preparation of the Phenoxy Phenyl Carbamates

Method 1

The product phenoxyphenyl carbamates can be prepared from theappropriate phenoxyalcohol intermediate and the appropriate phenylisocyanate in an inert solvent such as ether, methylene chloride, ortoluene. Catalysts such as 4-dimethylaminopyridine, triethylamine and/ordibutyltin dilaurate can be used. The reaction can be ran at roomtemperature or up to the reflux temperature of the reaction mixture. Thedesired product is isolated from the reaction media by evaporation undervacuum

Method 2

The product phenoxyphenyl carbamates can be prepared by reaction of theappropriate phenoxy chloroformate intermediate with the appropriateanaline in an inert solvent using an acid scavenger such as a tertiaryamine or pyridine. The reaction can be ran at -20° to 40° C. The productis isolated from the reaction mixture by washing with water and diluteacid to remove the by-product amine salt followed by evaporation of thesolvent to yield the desire product.

The following are examples of compounds which have been synthesized bythe procedures described above. These examples are offered strictly forpurposes of illustration, and are intended neither to limit nor todefine the invention in any manner.

EXAMPLE 1 Preparation of 1-(3-Trifluoromethylphenoxy)-2-butanol

A mixture of 3-trifluoromethylphenol (75 ml, 0.617 moles),1,2-epoxybutane (58 ml, 0.617 moles), potassium hydroxide pellets (86%,0.062 moles), and water (100 ml) were heated with stirring at 65° C. forfour hours. At this point more 1,2-epoxybutane (58 ml, 0.617 moles) wasadded and stirring at 65° C. continued overnight. The reaction wasallowed to cool to room temperature and the lower phase taken off andthe upper phase extracted with methylene chloride (2×100 ml). Theorganic phases were combined and washed with 5% sodium hydroxidesolution (150 ml) and water (3×150 ml). This reaction solution was driedover anhydrous magnesium sulfate and stripped under vacuo to yield 138 gof the desired alcohol, as determined by infra-red spectroscopy, massspectrometry and nuclear magnetic resonance spectroscopy.

EXAMPLE 2 Preparation of O-(3-Trifluoromethylphenoxy)-2-butylchloroformate

Phosgene (20% in toluene, 100 ml, 0.192 moles was added with stirring tothe alcohol of Example 1 (30 g, 0.128 moles) and toluene (75 ml) over aperiod of 10 minutes with cooling using a cold water bath. Next dimethylformamide (8 drops) was added. The reaction was heated to 50° C. atwhich temperature an exotherm occurred and the temperature maintained at55° C. for 4 hours with a dry ice condenser attached to the reactionflask. The next day further phosgene (20% in toluene, 20 ml, 0.038moles) was added and refluxing of the phosgene continued for 11/2 hoursto a maximum pot temperature of 80° C. Reaction cooled to roomtemperature and evaporated in vacuo to yield 37 g of an oil.

Gas chromatography of the product indicated 2% of the starting alcohol,7% of an unknown impurity and 88% of the desired product.

EXAMPLE 3

Preparation of O-[1-(3-trifluoromethylphenoxy)-2-butyl]N-(o-methylphenyl)-carbamate (Compound 16)

A solution of the alcohol of Example 1 (35.1 g, 0.15 moles), toluene(350 ml), o-tolyl isocyanate (18.6 ml, 0.15 moles), triethyl amine (3drops) and dibutyltin dilaurate (3 drops) was prepared. The solution washeated on the steam bath for 7 hours. Then the solvent was removed undervacuum and the resulting solid was washed with pentane to yield 48.9 gof white solid of the desired product Mp 75°-77° C. The structure of theproduct was confirmed by means of infra-red and nuclear magneticresonance spectroscopy and mass spectrometry.

EXAMPLE 4 Preparation ofO-[1-3-trifluoromethylphenoxy)-2-butyl]-N-(2-chloro-5-methylphenyl)-carbamate(Compound 47)

The chloroformate of Example 2 (2.96 g, 0.010 moles) was added to asolution in methylene chloride (125 ml) of 2-chloro-5-methyl aniline(1.27 g 0.009 moles) and pyridine (1.63 ml, 0.020 moles). The mixturewas allowed to stand over night at room temperature and then washed withwater (150 ml), 5% hydrochloric acid (100 ml), and 5% sodium bicarbonatesolution (150 ml); dried over anhydrous magnesium sulfate and evaporatedin vacuo to give an oil that was triturated with pentane to yield 1.7 gof white solid Mp 62°-64° C. The structure was confirmed by infra-redspectroscopy, nuclear magnetic resonance spectroscopy and massspectrometry.

                  TABLE I                                                         ______________________________________                                        COMPOUNDS                                                                      ##STR3##                                                                     Com-                                                                          pound                                                                         No.   R        R.sub.1  n   R.sub.2   m.p. °C.                         ______________________________________                                         1    CF.sub.3 CH.sub.3 2   2,5-F     104.5-106.0                              2    CF.sub.3 CH.sub.3 2   2,4-F     79.0-81.0                                3    CF.sub.3 CH.sub.3 1   2-F       81.0-83.5                                4    CF.sub.3 CH.sub.3 2   3-Cl, 4-F  98.0-101.0                              5    CF.sub.3 CH.sub.3 1   3-CF.sub.3                                                                              27.0-35.0                                6    CF.sub.3 CH.sub.3 1   2-CF.sub.3                                                                              81.0-83.0                                7    CF.sub.3 CH.sub.2 CH.sub.3                                                                      1   2-CF.sub.3                                                                              47.0-52.0                                8    CF.sub.3 CH.sub.2 CH.sub.3                                                                      2   2,5-F     Thick Yellow                                                                  Oil                                      9    CF.sub.3 CH.sub.2 CH.sub.3                                                                      1   2-F       Thick Yellow                                                                  Oil                                     10    CF.sub.3 CH.sub.2 CH.sub.3                                                                      1   3-CF.sub.3                                                                              Semi Solid                              11    NO.sub.2 CH.sub.2 CH.sub.3                                                                      2   2,4-F     104.0-106.0                             12    CF.sub.3 CH.sub.2 CH.sub.3                                                                      2   2,4-F     Thick Oil                               13    CF.sub.3 CH.sub.2 CH.sub.3                                                                      2   2,4-Cl    69.0-76.0                               14    CN       CH.sub.2 CH.sub.3                                                                      2   2,4-F     79.0-88.0                               15    Br       CH.sub.2 CH.sub.3                                                                      2   2,4-F     Semi-solid                              16    CF.sub.3 CH.sub.2 CH.sub.3                                                                      1   2-CH.sub.3                                                                              75-77° C.                        17    CF.sub.3 CH.sub.2 CH.sub.3                                                                      1   2-Cl                                              18    CF.sub.3 CH.sub.2 CH.sub.3                                                                      2   2-CF.sub.3, 4-Cl                                  19    CF.sub.3 CH.sub.2 CH.sub.3                                                                      2   2-CH.sub.3, 5-Cl                                  20    CF.sub.3 CH.sub.2 CH.sub.3                                                                      2   2,3-Cl                                            21    CF.sub.3 CH.sub.2 CH.sub.3                                                                      1   2-OCH.sub.3                                       22    CF.sub.3 CH.sub.2 CH.sub.3                                                                      2   3-Cl, 4-F                                         23    Br       CH.sub.2 CH.sub.3                                                                      1   2-CH.sub.3                                                                              96.0-97.0                               24    Br       CH.sub.2 CH.sub.3                                                                      1   2-CF.sub.3                                                                              62.0-64.0                               25    Br       CH.sub.2 CH.sub.3                                                                      1   2-Cl      Thick oil                               26    Br       CH.sub.2 CH.sub.3                                                                      2   2,3-Cl    Thick oil                               27    CF.sub.3 CH.sub.2 CH.sub.3                                                                      1   3-CN      Thick oil                               28    CF.sub.3 CH.sub.2 CH.sub.3                                                                      1   4-CN      Thick oil                               29    CF.sub.3 CH.sub.2 CH.sub.3                                                                      2   2-CH.sub.3, 5-Cl                                                                         97.0-102.0                             30    OCHF.sub.2                                                                             CH.sub.2 CH.sub.3                                                                      2   2,4-F     Thick oil                               31    OCHF.sub.2                                                                             CH.sub.2 CH.sub.3                                                                      1   2-CH.sub.3                                                                              Thick oil                               32    CN       CH.sub.3 1   2-CH.sub.3                                        33    CF.sub.3 CH.sub.2 CH.sub.3                                                                      2   2-CH.sub.3, 4-Cl                                  34    CF.sub.3 CH.sub.2 CH.sub.3                                                                      2   2-CH.sub.3, 3-Cl                                  35    CF.sub.3 CH.sub.2 CH.sub.3                                                                      2   2,5-F                                             36    CF.sub.3 CH.sub.2 CH.sub.3                                                                      2   2,6-F                                             37    CF.sub.3 CH.sub.2 CH.sub.3                                                                      2   3,4-Cl                                            38    CF.sub.3 CH.sub.2 CH.sub.3                                                                      1   2-OCH.sub.3                                       39    CF.sub.3 CH.sub.2 CH.sub.3                                                                      1   2-OCH.sub.2 CH.sub.3                              40    CF.sub.3 CH.sub.2 CH.sub.3                                                                      2   2-OCH.sub.3, 5-CH.sub.3                           41    CF.sub.3 CH.sub.2 CH.sub.3                                                                      2   2-CH.sub.3, 4-F                                                                         68.0-75.0                               42    CF.sub.3 CH.sub.2 CH.sub.3                                                                      3   2,4-F, 3-Cl                                                                             70.0-72.0                               43    CF.sub.3 CH.sub.2 CH.sub.3                                                                      2   2-F, 4-Cl 75.0-77.0                               44    CF.sub.3 CH.sub.2 CH.sub.3                                                                      2   2-Br, 4-F 71.0-74.0                               45    CF.sub.3 CH.sub.2 CH.sub.3                                                                      2   2,3-F     87.0-89.0                               46    CF.sub.3 CH.sub.2 CH.sub.3                                                                      2   2-CH.sub.3, 3-F                                                                         92.0-94.0                               47    CF.sub.3 CH.sub.2 CH.sub.3                                                                      2   2-Cl, 5-CH.sub.3                                                                        62.0-64.0                               48    CF.sub.3 CH.sub.2 CH.sub.3                                                                      1   2-CN      73.0-76.0                               ______________________________________                                    

The compounds listed in the foregoing table were tested for herbicidalactivity by various methods and at various rates for application. Theresults of some of these tests are given below. As one skilled in theart is aware, the results obtained in herbicidal screening tests areaffected by a number of factors that are not readily controllable.Environmental conditions, such as amount of sunlight and water, soiltype, soil pH, temperature and humidity, are examples of such factors.The depth of planting and the application rate of the herbicide, as wellas the nature of crops being tested, can also affect the test results.Results will also vary from crop to crop and within the crop varieties.

The test procedures used are as follows:

Pre-Emergence Herbicidal Evaluation at 4 lb/acre

Planting flats were filled with sandy loam soil containing a fungicideand fertilizer. The soil was leveled and (Cyperus esculentus), wereplanted thickly enough so that several seedlings emerged per inch ofrow. The grassy weeds were green foxtail (Setaria viridis), watergrass(Echinocloa crusgalli) and wild oat (Avena fatua). Broadleaf weedsutilized were annual morningglory (Ipomoea purpurea), velvet-leaf(Abutilon theophrasti) and wild mustard (Brassica kaber).

Solutions of the test compounds were made by weighing out 333.0 mg ofthe test compound into a 60 ml wide-mouth bottle, then dissolving thecompound in 25 ml of acetone containing 1% Tween® 20 (polyoxyethlenesorbitan monolaurate emulsifier). Additional solvents, not exceeding 5ml, were used if needed to dissolve the compound. A 20.5 ml aliquot wasthen taken from the solution and diluted with 25 ml of an acetone:watermixture (19:1) containing 1% Tween® 20. This was used as the spraysolution.

One day after plantinq, the flats were sprayed with the spray solutionat a rate of 80 gallons of solution per acre with the compound beingapplied at a rate of 4 lb/acre (4.48 kg/hectare).

The flats were then returned to the greenhouse and watered daily bysprinkling. The degree of weed control was estimated and recorded 3weeks after treatment, as percentage control compared to the growth ofthe same species in an untreated check flat of the same age.

The percent control is the total injury to the plants due to allfactors, including inhibited germination, killing of the plant tissueafter emergence, stunting, malformation, chlorosis, and other types ofinjury. The control ratings vary from 0 to 100 percent, where 0represents no effect with growth equal to the untreated control, and 100represents complete kill; a dash indicates that no test was performed atthat level of application.

Post-Emergence Herbicidal Evaluation at 4 lb/acre

The soil was prepared and seeded with the same varieties used in thepre-emergence test. The flats were placed in the greenhouse at 70°-85°C.) (21°-29° C.) and watered by sprinkling. Twelve to fourteen daysafter planting, the flats were sprayed at a rate of 80 gallons ofsolution per acre. Each compound was applied at the rate of 4 lb/acre(4.48 kg/hectare), using a spray solution prepared as in thepre-emergence test.

The flats were returned to the greenhouse after spraying and watereddaily without wetting the foliage. Three weeks after treatment thedegree of weed control was estimated and recorded as percentage controlcompared to the growth of the same species in an untreated check flat ofthe same age. The percent control ratings were assigned on the saidbasis as for the pre-emergence evaluation.

Solutions of the test compounds for rates of application of 2 lb/acre(2.24 Kg/hectare), 3.57 lb/acre (4 Kg/hectare) and 1.78 lb/acre (2 Kghectare) were applied as described above and were prepared as follows:

A) Solutions of the test compounds tested at 2 lb/acre (2.24 Kg/hectare)were made by weighing out 120 mg of the test compound into a 60 mlwide-mouth bottle, then dissolving the compound in 20 ml of acetonecontaining 1% Tween® 20 (polyoxyethlene sorbitan monolaurate emulsifier)and 20 ml of distilled water. Additional solvents, not exceeding 5 ml,were used if needed to dissolve the compound. This solution was used asthe spray solution;

B) Solutions of the test compounds tested at 3.57 lb/acre (4 Kg/hectare)were made by weighing out 160 mg of the test compound into a 60 mlwide-mouth bottle, then dissolving the compound in 15 ml of acetonecontaining 1% Tween® 20 (polyoxyethlene sorbitan monolaurate emulsifier)and 15 ml of distilled water. Additional solvents, not exceeding 5 ml,were used if needed to dissolve the compound. This solution was used asthe spray solution;

C) Solutions of the test compounds tested at 1.78 lb/acre (2 Kg/hectare)were made by weighing out 80 mg of the test compound into a 60 mlwide-mouth bottle, then dissolving the compound in 15 ml of acetonecontaining 1% Tween® 20 (polyoxyethlene sorbitan monolaurate emulsifier)and 15 ml of distilled water. Additional solvents, not exceeding 5 ml,were used if needed to dissolve the compound. This solution was used asthe spray solution;

The following table lists the results of these tests, in terms ofaverages for the grasses and broadleaf weeds, with yellow nutsedgelisted separately, in both pre- and post-emergence evaluations.

                  TABLE II                                                        ______________________________________                                        HERBICIDE TEST RESULTS                                                        PERCENT CONTROL AT 4 LB/ACRE                                                  Abreviations:                                                                 YNS: Yellow Nutsedge                                                          AVG: Grasses averaged                                                         AVB: Broadleaf weeds averaged                                                 Compound Pre-Emergence   Post Emergence                                       No.      YNS     AVG     AVB   YNS   AVG   AVB                                ______________________________________                                        1        0       37      20    0     0     23                                 2        0       92      73    0     53    85                                 3        0       65      57    0     40    67                                 4        0       37      43    0     0     50                                 5        0       63      50    0     0     50                                 6        0       47      43    0     0     67                                 7        0       100     90    0     88    100                                8        0       93      93    0     75    90                                 9        0       97      95    0     85    80                                 10       0       40      40    0     0     53                                 11       0       70      67    0     30    50                                 12       0       73      73    0     33    80                                 13       0       33      33    0     0     20                                 14       0       73      100   30    60    67                                 15       0       83      67    0     73    60                                 16*      0       100     100   40    97    95                                 17*      0       93      100   0     60    80                                 18*      0       57      43    0     40    53                                 19*      0       93      80    0     47    73                                 20*      0       100     100   0     63    67                                 21*      0       85      40    0     23    33                                 22*      0       0       0     0     0     73                                 23**     0       83      93    0     63    50                                 24**     0       77      43    0     55    37                                  25***   0       83      80    0     60    40                                 26**     0       70      47    0     43    50                                 27**     0       0       0     0     7     60                                 28**     0       0       0     0     0     23                                 29**     0       30      47    0     27    67                                 30**     0       67      57    0     27    83                                 31**     0       90      73    0     40    83                                 32**     80      73      100   --    53    80                                 33**     0       67      70    0     50    80                                 34**     --      90      98    0     60    80                                 35**     0       77      63    0     77    97                                 36**     0       50      70    0     47    80                                 37**     0       40      43    0     10    83                                 38**     0       43      47    0     43    33                                 39**     0       7       17    0     0     27                                 40**     0       0       0     0     0     13                                  41***   30      100     100   40    90    100                                 42***   0       73      73    --    67    100                                 43***   --      47      40    0     23    85                                  44***   --      47      77    --    13    50                                  45***   --      77      90    0     80    83                                  46***   0       100     100   0     90    90                                  47***   0       27      57    0     23    43                                  48***   --      60      80    0     30    95                                 ______________________________________                                         *indicates compound tested at 2 lb/acre                                       **indicates compound tested at 1.78 lb/acre                                   ***indicates compound tested at 3.57 lb/acre                             

The compounds of the present invention are useful as herbicides and canbe applied in a variety of ways known to those skilled in the art, atvarious concentrations. In practice, the compounds are applied asformulations containing the various adjuvants and carriers known to orused in the industry for facilitating dispersion. The choice offormulation and mode of application for any given compound may affectits activity, and selection will be made accordingly. The compounds ofthe invention may thus be formulated as granules, as wettable powders,as emulsifiable concentrates, as powders or dusts, as flowables, assolutions, suspensions or emulsions, or in controlled-released formssuch as micro-capsules. These formulations may contain as little asabout 0.5% to as much as about 95% or more by weight of activeingredient. The optimum amount for any given compound will depend uponthe nature of the seeds or plants to be controlled. The rate ofapplication will generally vary from about 0.01 to about 10 lb/acre,preferably from about 0.02 to about 4 lb/acre.

Wettable powders are finely divided particles which disperse readily inwater or other liquid carriers. The particles contain the activeingredient retained in a solid matrix. Typical solid matrices includefuller's earth, kaolin clays, silicas and other readily wet organic orinorganic solids. Wettable powders normally contain about 5% to about95% of the active ingredient plus a small amount of wetting, dispersing,or emulsifying agent.

Emulsifiable concentrates are homogeneous liquid compositionsdispersible in water or other liquid, and may consist entirely of theactive compound with a liquid or solid emulsifying agent, or may alsocontain a liquid carrier, such as xylene, heavy aromatic naphthas,isophorone and other nonvolatile organic solvents. In use, theseconcentrates are dispersed in water or other liquid and normally appliedas a spray to the area to be treated. The amount of active ingredientmay range from about 0.5% to about 95% of the concentrate.

Granular formulations include both extrudates and relatively coarseparticles, and are usually applied without dilution to the area in whichsuppression of vegetation is desired. Typical carriers for granularformulations include sand, fuller's earth, attapulgite clay, bentoniteclays, montmorillonite clay, vermiculite, perlite and other organic orinorganic materials which absorb or which can be coated with the activecompound. Granular formulations normally contain about 5% to about 25%active ingredients which may include surface-active agents such as heavyaromatic naphthas, kerosene or other petroleum fractions, or vegetableoils; and/or stickers such as dextrins, glue or synthetic resins.

Dusts are free-flowing admixtures of the active ingredient with finelydivided solids such as talc, clays, flours and other organic andinorganic solids which act as dispersants and carriers.

Microcapsules are typically droplets or granules of the active materialenclosed in an inert porous shell which allows escape of the enclosedmaterial to the surroundings at controlled rates. Encapsulated dropletsare typically about 1 to 50 microns in diameter. The enclosed liquidtypically constitutes about 50 to 95% of the weight of the capsules, andmay include solvent in addition to the active compound. Encapsulatedgranules are generally porous granules with porous membranes sealing thegranule pore openings, retaining the active species in liquid forminside the granule pores. Granules typically range from 1 millimeter to1 centimeter, preferably 1 to 2 millimeters in diameter. Granules areformed by extrusion, agglomeration or prilling, or are naturallyoccurring. Examples of such materials are vermiculite, sintered clay,kaolin, attapulgite clay, sawdust and granular carbon. Shell or membranematerials include natural and synthetic rubbers, cellulosic materials,styrene-butadiene copolymers, polyacrylonitriles, polyacrylates,polyesters, polyamides, polyureas, polyurethanes and starch xanthates.

Other useful formulations for herbicidal applications include simplesolutions of the active ingredient in a solvent in which it iscompletely soluble at the desired concentration, such as acetone,alkylated napthalenes, xylene and other organic solvents. Pressurizedsprays, wherein the active ingredient is dispersed in finely-dividedform as a result of vaporization of a low boiling dispersant solventcarrier, such as the Freons, may also be used.

Many of these formulations include wetting, dispersing or emulsifyingagents. Examples are alkyl and alkylaryl sulfonates and sulfates andtheir salts; polyhydric alcohols; polyethoxylated alcohols; esters andfatty amines. These agents when used normally comprise from 0.5% to 15%by weight of the formulation.

The compounds of the present invention are also useful when combinedwith other herbicides and/or defoliants, desiccants, growth inhibitors,and the like. These other materials can comprise form about 5% to about95% of the active ingredients in the formulations. These combinationsfrequently provide a higher level of effectiveness in controlling weedsand often provide results unattainable with separate formulations of theindividual herbicides.

Examples of other herbicides, defoliants, desiccants and plant growthinhibitors with which the compounds of this invention can be combinedare:

chlorophenoxy herbicides such as 2,4-D, 2,4,5-T, MCPA, MCPB, 2,4-DB,2,4-DEB, 4-CPA, 2,4,5-TB, and silvex;

carbamate herbicides such as propham, chlorpropham swep, and barban;

thiocarbamate and dithiocarbamate herbicides such as CDEC,metham-sodium, EPTC, diallate, PEBC, and vernolate;

substituted urea herbicides such as norea, dichloral urea, chloroxuron,cycluron, fenuron, monuron, monuron TCA, diuron, linuron, monolinuronneburon, buturon and trimeturon;

symmetrical triazine herbicides such as simazine, chlorazine,desmetryne, norazine, ipazine, prometryn, atrazine, trietazine,simetone, prometone, propazine and ametryne;

chlorinated aliphatic acid herbicides such as TCA and dalapon;

chlorinated benzoic acid and phenylacetic acid herbicides such as2,3,6-TBA, dicamba, tricamba, chloramben, fenac, PBA,2-methoxy-3,6-dichlorophenylacetic acid,3-methoxy-2,6-dichlorophenylacetic acid,2-methoxy-3,5,6-trichlorophenylacetic acid and2,4-dichloro-3-nitrobenzoic acid;

and such compound as aminotriazole, maleic hydrazide, phenylmercuryacetate, endothal, technical chlordane, CDPA, diquat, erbon, DNC, DNBP,dichlobenil, DPA, diphenamide, dipropalin, trifluralin, solan, dicryl,merphos, DMPA, DSMA, MSMA, potassium azide, acrolein, benefin,bensulide, AMS, bromacil,2-(3,4-dichlorophenyl)-4-methyl-1,2,4-oxazolidine-3,5-dione, bromoxynil,cacodylic acid, CMA, CPMF, cypromid, DCB, DCPA, dichlone, diphenatril,DMTT, DNAP, EBEP, EXD, HCA, ioxynil, IPX, isocil, potassium cyanate,MAA, MAMA, MCPES, MCPP, MH, molinate, NPA, OCH, paraquat, PCP, picloram,DPA, PCA, sesone, terbacil, terbutol, TCBA, alachlor, nitralin, sodiumtetraborate, calcium cyanamide, S,S,S-tributylphosphorotrithioate andpropanil.

These formulations can be applied to the areas where control is desiredby conventional methods. Dust and liquid compositions, for example, canbe applied by the use of powerdusters, boom and hand sprayers and spraydusters. The formulations can also be applied from airplanes as a dustor a spray or by rope wick applications. To modify or control growth ofgerminating seeds or emerging seedlings, dust and liquid formulationscan be distributed in the soil to a depth of at least one-half inchbelow the soil surface or applied to the soil surface only, by sprayingor sprinkling. The formulations can also be applied by addition toirrigation water. This permits penetration of the formulations into thesoil together with the irrigation water. Dust compositions, granularcompositions or liquid formulations applied to the surface of the soilcan be distributed below the surface of the soil by conventional meanssuch as discing, dragging or mixing operations.

The following are examples of typical formulations.

5% dust

5 parts active compound

95 parts talc

2% dust

2 parts active compound

1 part highly dispersed silicic acid

97 parts talc

These dusts are formed by mixing the components then grinding themixture to the desired particle size.

5% granules

5 parts active compound

0.25 part epichlorohydrin

0.25 part cetyl polyglycol ether

3.5 parts polyethylene glycol

91 parts kaolin (particle size 0.3-0.8 mm)

Granules are formed by mixing the active compound with epichlorohydrinand dissolving the mixture in 6 parts of acetone. The polyethyleneglycol and cetyl polyglycol ether are then added. The resultant solutionis sprayed on the kaolin and the acetone evaporated in vacuo.

wettable powders 70%

70 parts active compound

5 parts sodium dibutylnaphthylsulfonate

3 parts naphthalenesulfonic acid/phenosulfonic acid/formaldehydecondensate (3:2:1)

10 parts kaolin

12 parts Champagne chalk

40%

40 parts active compound

5 parts sodium lignin sulfonate

1 part sodium dibutylnaphthalenesulfonic acid

54 parts silicic acid

25%

25 parts active compound

4.5 parts calcium lignin sulfate

1.9 parts Champagne chalk/hydroxyethyl cellulose (1:1)

1.5 parts sodium dibutylnaphthalenesulfonate

19.5 parts silicic acid

19.5 parts Champagne chalk

28.1 parts kaolin

25%

25 parts active compound

2.5 parts isooctylphenoxy-polyethyleneethanol

1.7 parts Champagne chalk/hydroxyethyl cellulose (1.1)

8.3 parts sodium aluminum silicate

16.5 parts kieselguhr

46 parts kaolin

10%

10 parts active compound

3 parts of a mixture of sodium salts of saturated fatty alcohol sulfates

5 parts naphthalenesulfonic acid/formaldehyde condensate

82 parts kaolin

These wettable powders are prepared by intimately mixing the activecompounds with the additives in suitable mixers, and grinding theresulting mixtures in mills or rollers.

25% emulsifiable concentrate

25 parts active substance

2.5 parts epoxidized vegetable oil

10 parts of an alkylarylsulfonate/fatty alcohol polyglycol ether mixture

5 parts dimethylformamide

57.5 parts xylene

What is claimed is:
 1. A method of controlling undesirable vegetationcomprising applying to said vegetation or to the locus thereof anherbicidally effective amount of a compound having the formula ##STR4##in which: R is a member selected from the group consisting oftrifluoremethyl and C₁ -C₃ C₁ -C₃ haloalkyloxy;R₁ is methyl or ethyl; R₂is independently selected from the group consisting of cyano, halogen,C₁ -C₄ alkyl, C₁ -C₄ alkoxy and C₁ -C₄ haloalkyl; and n is the number ofR₂ substituents and equals 1-5.
 2. A method according to claim 1 whereinR is CF₃, R₁ is CH₃, R₂ is 2,5-F and n is
 2. 3. A method according toclaim 1 wherein R is CF₃, R₁ is CH₂ CH₃, R₂ is 2,4-F and n is
 2. 4. Amethod according to claim 1 wherein R is CF₃, R₁ is CH₂ CH₃, R₂ is 2-CH₃and n is
 1. 5. A method according to claim 1 wherein R is CF₃, R₁ is CH₂CH₃, R₂ is 2-CH₃, 5-Cl and n is 2.